JPH02116603A - Method for reforming methanol - Google Patents
Method for reforming methanolInfo
- Publication number
- JPH02116603A JPH02116603A JP26938988A JP26938988A JPH02116603A JP H02116603 A JPH02116603 A JP H02116603A JP 26938988 A JP26938988 A JP 26938988A JP 26938988 A JP26938988 A JP 26938988A JP H02116603 A JPH02116603 A JP H02116603A
- Authority
- JP
- Japan
- Prior art keywords
- carrier
- catalyst
- contg
- methanol
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims description 10
- 238000002407 reforming Methods 0.000 title description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract description 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 18
- 230000000694 effects Effects 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
Landscapes
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はメタノールの改質方法に関し、特にメタノール
と酸素含有ガスとを反応させて低温かつ、長時間安定し
て水素含有ガスを製造するメタノール改質方法に関する
。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for reforming methanol, and in particular to a method for reforming methanol, in which methanol and oxygen-containing gas are reacted to produce hydrogen-containing gas stably at low temperatures and over a long period of time. Regarding modification methods.
メタノールは石炭、天然ガスなどから合成ガスを経由し
て大規模に製造することができ、しかも輸送が容易であ
ることから、将来、石油に代るエネルギー源あるいは種
々化学工業原料として大きな関心がもたれている。Methanol can be produced on a large scale from coal, natural gas, etc. via synthetic gas, and is easy to transport, so it is of great interest in the future as an energy source to replace petroleum or as a raw material for various chemical industries. ing.
その利用法の一つとしてメタノールを水素含有ガスに改
質させて、これを自動車用無公害燃料あるいは燃料電池
用燃料として利用する方法がある。One method of using it is to reform methanol into a hydrogen-containing gas and use this as a pollution-free fuel for automobiles or fuel for fuel cells.
メタノールから水素含有ガスを製造する反応としては、
一般に次の反応が用いられる。As a reaction to produce hydrogen-containing gas from methanol,
Generally the following reactions are used.
上記反応は吸熱反応であるため、熱源が必要である。従
って一般に多管式反応器が用いられておシ、反応管に触
媒を充填し、反応管外に熱媒を通すことによシ反応熱が
供給されるため、熱効率が低いという欠点がある。また
熱力学平衡上、転化率を９５％以上にするためには反応
温度を２５０°Ｃ以上にする必要がちシ、スタートアッ
プに時間がかかるという問題点もある。Since the above reaction is an endothermic reaction, a heat source is required. Therefore, a multi-tubular reactor is generally used, but the reaction heat is supplied by filling the reaction tube with a catalyst and passing a heating medium outside the reaction tube, which has the disadvantage of low thermal efficiency. Furthermore, in terms of thermodynamic equilibrium, in order to achieve a conversion rate of 95% or higher, the reaction temperature tends to be 250° C. or higher, and there is also the problem that it takes time to start up.
上記問題点を解決する方法として、次の部分酸化反応を
利用した改質反応が考えられる。As a method for solving the above problems, a modification reaction using the following partial oxidation reaction can be considered.
ＣＨ３０Ｈ＋３ＡＯ１（＋２Ｎり→Ｃｏ、＋２Ｈ，（＋
２Ｎ、） −・−■ＣＨｓＯＨ＋ｙ４０ｍ ＋３Ａ Ｈ
ｚＯ（＋Ｎ！ ） →Ｃｏｔ ＋ 、 Ｈ宜（＋Ｎｔ
） ”−■また特開昭５２−１５６１９４号公報などで
は次のような部分酸化反応■及びその反応用の触媒（γ
−ア〜ミナにＮｉ、 Ｃｒ、 Ｃｕを担持した触媒）が
提案をされているが、 ＣＨ４の生成など選択性がよく
ないこと、かつ触媒の長期安定性に欠けるという問題点
のあることがわかった。CH30H+3AO1(+2Nri→Co,+2H,(+
2N,) -・-■CHsOH+y40m +3A H
zO(+N!) →Cot +, H yi(+Nt
) ”-■ Also, in JP-A-52-156194, etc., the following partial oxidation reaction ■ and a catalyst for the reaction (γ
-Catalysts with Ni, Cr, and Cu supported on alumina have been proposed, but it has been found that they have problems such as poor selectivity such as CH4 production and lack of long-term stability of the catalyst. Ta.
Ｃ）（３０Ｈ＋（Ｌｌ ５０． ＋ＣＬ６Ｎ、 ４１．
６５Ｈ！＋Ｑ、７５ＣＯ＋（ＬＩ ＣＨ４＋ａ１５Ｈ，
０−１４１５ｃｏ、十（Ｌ６Ｎ！−・・■〔課題を解決
するための手段〕
そこで、本発明者らはメタノ−Ａ／１モμ当たりのＨ２
発生量が２七μ以上になる反応■、■（従来の反応■で
は馬発生盪１．６５モ／Ｌ／）を選択的にかつ、低温で
進行させるための触媒の開発を行った。すなわち、担体
を塩基性にすることにより副反応が抑制されることに着
目し、種々の実験検討を重ねた結果、希土類元素の酸化
物を含有する担体に白金及び／又はパラジウムを担持さ
せた触媒が、メタノールの改質反応■。C) (30H+(Ll 50. +CL6N, 41.
65H! +Q, 75CO+(LI CH4+a15H,
0-1415co, 10(L6N!-...■ [Means for solving the problem]) Therefore, the present inventors determined that H2 per methano-A/1 moμ
We have developed a catalyst for selectively and at low temperatures the reactions ① and ② that generate 27μ or more (compared to 1.65μ/L/in the conventional reaction ②). Specifically, we focused on the fact that side reactions can be suppressed by making the support basic, and as a result of various experimental studies, we have developed a catalyst in which platinum and/or palladium is supported on a support containing an oxide of a rare earth element. However, the methanol reforming reaction ■.
■において、活性、選択性、耐久性とも極めて優れてい
ることを見出し、本発明を完成するに至った。In (2), it was discovered that the activity, selectivity, and durability were extremely excellent, and the present invention was completed.
すなわち、本発明はメタノールと酸素含有ガスとを反応
させて水素含有ガスを製造する方法において、希土類元
素の酸化物を含有する担体上に白金及び／又はパラジウ
ムを担持させた触媒を用いることを特徴とするメタノー
ル改質方法である。That is, the present invention is characterized in that a method for producing a hydrogen-containing gas by reacting methanol and an oxygen-containing gas uses a catalyst in which platinum and/or palladium is supported on a carrier containing an oxide of a rare earth element. This is a methanol reforming method.
本発明のメタノール改質方法における好ましい反応条件
は、次の通りである。Preferred reaction conditions in the methanol reforming method of the present invention are as follows.
反応温度：１００〜６００°Ｃ特に好ましくは２００〜
５００℃
メタノ−ｆｖ１七〜に対する空気供給モル比：α１〜５
特に好ましくは０．５〜２
メタノ−／Ｓ／１モＭに対する水の供給モル比：（ＬＯ
１〜１０特に好ましくは０．１〜２触媒１Ｌに対するメ
タノール供給ｔｔＡＸ： Ｑ、１〜１０特に好ましくは
α５〜５
こ−で希土類元素の酸化物とは、周期律表のＩｎａ族の
希土類元素の酸化物であシ、例えば酸化フンタン（Ｌａ
＊Ｏｓ）、酸化セリウム（Ｃｅ ０２）、酸化ネオジウ
ム（Ｎｄ！０１） 又はこれらの混合物などがあげら
れる。Reaction temperature: 100-600°C, particularly preferably 200-600°C
500℃ Air supply molar ratio to methanol-fv17~: α1~5
Particularly preferably 0.5 to 2 molar ratio of water to methanol/S/1 moM: (LO
1-10 Particularly preferably 0.1-2 Methanol supply per 1 L of catalyst ttAX: Q, 1-10 Particularly preferably α5-5 Here, the rare earth element oxide refers to a rare earth element of the Ina group of the periodic table. Oxides, such as funtan oxide (La
*Os), cerium oxide (Ce 02), neodymium oxide (Nd! 01), or a mixture thereof.
また、ここで希土類元素の酸化物を含有する担体とは、
希土類元素の酸化物を、少なくとも１市世％以上、好ま
しくは１０〜９８重量％（担体全ｉｔ基準）含有する担
体であり、希土類元素の酸化物以外の物質として、アμ
ミナ、チタニア、ジルコニア、シリカその他バインダー
成分などを含有するものをさす。In addition, here, the carrier containing the oxide of a rare earth element is
A carrier containing an oxide of a rare earth element at least 1% by weight, preferably 10 to 98% by weight (based on the total weight of the carrier), and as a substance other than the oxide of a rare earth element,
Refers to materials containing mina, titania, zirconia, silica, and other binder components.
一例としてはＬａ２０１Ａｔ２０１ 、 Ｌａ１０３−
Ｔｉ０２ 、 Ｃｅ０１−Ａ／４０３ 、 Ｃｅ０ｌ−
８１０１，Ｎｄ１０３−Ａ／１０１ 、 Ｎｄ４０３−
ＺｒＯｌ 。Examples include La201At201, La103-
Ti02, Ce01-A/403, Ce0l-
8101, Nd103-A/101, Nd403-
ZrOl.
Ｌａ２Ｏ２−Ｃｅ Ｏ意・Ａｌ４ｏ３ などの組み合わ
せがある。There are combinations such as La2O2-CeO and Al4o3.
Ｌａ２０ｇ−ＡＩ４０３担体を例としてその調製法を説
明すると、
■ アμミナ担体を硝酸ランタンの水溶液に浸漬する、
■ Ｌａｇ○ｓ、Ｌａｗ（ＣＯｓ）ｓなどと１ペナゾμ
と混合する。The preparation method using La20g-AI403 carrier as an example is as follows: 1) Immersing the Amina carrier in an aqueous solution of lanthanum nitrate; 2) Coating with Lag○s, Law(COs)s, etc.
Mix with.
■ Ｌａ化合物含有水溶液とｋＡ化合物含有水溶液の混
合液に炭峻ソーダなどのアルカリを加えて沈殿をつくる
。■ Add an alkali such as carbonated soda to a mixture of an aqueous solution containing a La compound and an aqueous solution containing a kA compound to form a precipitate.
以上いずれかの工程の後、乾燥焼成することにより容易
に得られる。After any of the above steps, it can be easily obtained by drying and firing.
次にこのようにして得られた担体に白金及びパラジウム
を担持させる方法は従来から用いられている方法で問題
なく、例えば白金及び／又はパラジウムの硝酸塩、又は
塩化物、アンミン錯体などの化合物の水浴液に担体を浸
漬した後、焼成し、さらにそれを水素還元処理すれば白
金及び／又はパラジウムが担持された触媒が得られる。Next, the method of supporting platinum and palladium on the carrier obtained in this way can be any conventionally used method, such as a water bath of a compound such as platinum and/or palladium nitrate, chloride, ammine complex, etc. After immersing the carrier in the liquid, it is calcined and further subjected to hydrogen reduction treatment to obtain a catalyst on which platinum and/or palladium is supported.
白金及び／又はパラジウムの担持量（担体基準）は、（
１０１〜１０選量％の範囲が好ましい。The supported amount of platinum and/or palladium (based on carrier) is (
A range of 101 to 10% is preferred.
以上のようにしで得られた触媒は、メタノールと酸素含
有ガスとを反応させて水素含有ガスを製造する反応に対
し、高選択性でかつ活性が高く、耐久性にも極めて優れ
た性能を有するものである。The catalyst obtained as described above has high selectivity and activity for the reaction of methanol and oxygen-containing gas to produce hydrogen-containing gas, and has extremely excellent durability. It is something.
以下、実施例によシ、本発明を具体的に説明する。Hereinafter, the present invention will be specifically explained using examples.
〔実施例１〕
酸化ランタン（Ｌａｗ’ｓ）粉末とアμミナゾルを混合
し、乾燥後５００℃で５時間焼成してＬａ４０３とＡｌ
４０ｓ の重量比９０：１０のＬａｇ ０３ ” Ａ４
０３担体を得た。[Example 1] Lanthanum oxide (Law's) powder and amimina sol were mixed, dried and fired at 500°C for 5 hours to form La403 and Al.
40s weight ratio 90:10 Lag 03” A4
03 carrier was obtained.
このようにして得られた担体をテトラアンミン、二塩化
白金〔化学式Ｐｔ （ＮＨ２）４ＣＩ４）の水溶液に浸
漬し、乾燥後５００°Ｃで３時間焼成して、（Ｌ ５
ｔＢ址％の白金を担持した触媒１を調製した。The carrier thus obtained was immersed in an aqueous solution of tetraammine and platinum dichloride [chemical formula Pt (NH2)4CI4], dried and then calcined at 500°C for 3 hours to obtain (L 5
Catalyst 1 supporting tB% of platinum was prepared.
この触媒を４００°Ｃで３時間、４％水素気流中で還元
し表１に示す条件で活性評価試験を行い、表２の結果を
得た。なお比較触媒として、従来のγ−ＡＩ４０３担体
に白金を１５重量％担持した比較触媒１、またＣｕＯ１
８重量％、 ＮｉＯ９ｉｉｉ％。This catalyst was reduced at 400° C. for 3 hours in a 4% hydrogen stream, and an activity evaluation test was conducted under the conditions shown in Table 1. The results shown in Table 2 were obtained. As comparative catalysts, Comparative Catalyst 1 in which 15% by weight of platinum was supported on a conventional γ-AI403 carrier, and CuO1
8% by weight, NiO9iii%.
Ｃｒ２０ｇ ３直置％（担体基準）担持した比較触媒２
を調製し、反応温度３００°Ｃでの活性評価試験を行っ
た結果を併せて表２に示した。Comparative catalyst 2 supported with 20g Cr 3% (based on carrier)
was prepared and subjected to an activity evaluation test at a reaction temperature of 300°C. The results are also shown in Table 2.
〔実施例２〕
実施例１で調製した触媒１と同じ方法で、Ｌａ！０３の
濃度（担体全量基準）それぞれ１０３０．５０，７０．
９５重１ｔ％になるように担体を副製し、これを塩化白
金酸水溶液に浸漬し、水素還元処理を行って白金が１３
電量％になるように担持した触媒２〜６を調製した。[Example 2] In the same manner as Catalyst 1 prepared in Example 1, La! The concentrations of 03 (based on the total amount of carrier) were 1030.50 and 70.
A carrier is produced as a by-product with a weight of 95% by weight and 1t%, which is immersed in a chloroplatinic acid aqueous solution and subjected to hydrogen reduction treatment to reduce platinum to 13% by weight.
Catalysts 2 to 6 were prepared which were supported so as to have a coulometric percentage.
これらの触媒について、反応温度を３００℃にした以外
は表１に示す条件で活性評価試験を行い、表３の結果を
得た。Regarding these catalysts, an activity evaluation test was conducted under the conditions shown in Table 1 except that the reaction temperature was 300°C, and the results shown in Table 3 were obtained.
表 ３
〔実施例３〕
アルミナ担体を硝酸セリウム水溶液に浸漬し、乾燥、焼
成を行い、 Ｃｅ０１の濃度１０改盪％（担体全量基準
）担持し九Ｃｅ０ｌ−ＡＩ４０３担体をジニトロジアミ
ン白金硝酸性溶液に浸漬し、水素還元処理を行って白金
濃度が、α１．（Ｌ３．Ｑ、５゜１直置％になるよう担
持した触媒７〜１０及び同様の方法でバヲジウム濃度が
、（Ｌｌ、α５重ｔ％になるよう担持した触媒１１１２
を、さらにアルミナにＮｄｔＯｓ ６度１０重量％担持
したＮｄ意０ｓ−ＡＴＯｓ担体を用いて白金濃度１３重
′ｋｋ％、パフジクム濃度１２道量％になるように担持
した触媒１３を調製した。Table 3 [Example 3] An alumina carrier was immersed in a cerium nitrate aqueous solution, dried, and calcined to support a Ce01 concentration of 10% (based on the total amount of the carrier). After immersion and hydrogen reduction treatment, the platinum concentration was reduced to α1. (L3.Q, 5゜Catalysts 7 to 10 supported so as to be 1% directly, and catalyst 1112 supported so that the Baodium concentration was (Ll, α5% by weight) in a similar manner.
Catalyst 13 was prepared by using a NdOs-ATOs carrier in which NdtOs was supported on alumina in an amount of 6% by weight and 10% by weight to give a platinum concentration of 13% by weight and a platinum concentration of 12% by weight.
これらの触媒について反応温度を３００°Ｃにした以外
は表１に示す条件と同じ方法で活性評価試験を行い、表
４の結果を得た。Activity evaluation tests were conducted on these catalysts under the same conditions as shown in Table 1, except that the reaction temperature was 300°C, and the results shown in Table 4 were obtained.
表 ４
なお、触媒９について、約４０００時間の耐久性試験を
行ったが、活性の低下はみられなかった。Table 4 Note that although a durability test of about 4000 hours was conducted on Catalyst 9, no decrease in activity was observed.
本発明によシ、メタノールと酸素を含有するガスから水
素濃度の高い水素含有ガスを低温かつ、選択性よく長時
間安定して！！！迫することができる。According to the present invention, a hydrogen-containing gas with a high hydrogen concentration can be produced stably for a long time with good selectivity at a low temperature from a gas containing methanol and oxygen! ! ! can be approached.
Claims (1)
を製造する方法において、希土類元素の酸化物を含有す
る担体上に白金及び／又はパラジウムを担持させた触媒
を用いることを特徴とするメタノール改質方法。A method for producing a hydrogen-containing gas by reacting methanol and an oxygen-containing gas, characterized in that a catalyst in which platinum and/or palladium is supported on a carrier containing an oxide of a rare earth element is used. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26938988A JPH02116603A (en) | 1988-10-27 | 1988-10-27 | Method for reforming methanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26938988A JPH02116603A (en) | 1988-10-27 | 1988-10-27 | Method for reforming methanol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02116603A true JPH02116603A (en) | 1990-05-01 |
Family
ID=17471726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26938988A Pending JPH02116603A (en) | 1988-10-27 | 1988-10-27 | Method for reforming methanol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02116603A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6397790B1 (en) | 2000-04-03 | 2002-06-04 | R. Kirk Collier, Jr. | Octane enhanced natural gas for internal combustion engine |
| US6405720B1 (en) | 2000-04-03 | 2002-06-18 | R. Kirk Collier, Jr. | Natural gas powered engine |
| CN1098123C (en) * | 1999-08-18 | 2003-01-08 | 中国科学院山西煤炭化学研究所 | Methyl alcohol low-temp. cracking catalyst |
| US6508209B1 (en) | 2000-04-03 | 2003-01-21 | R. Kirk Collier, Jr. | Reformed natural gas for powering an internal combustion engine |
| US8025861B2 (en) | 2005-08-12 | 2011-09-27 | GM Global Technology Operations LLC | Making electrocatalyst supports for fuel cells |
-
1988
- 1988-10-27 JP JP26938988A patent/JPH02116603A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1098123C (en) * | 1999-08-18 | 2003-01-08 | 中国科学院山西煤炭化学研究所 | Methyl alcohol low-temp. cracking catalyst |
| US6397790B1 (en) | 2000-04-03 | 2002-06-04 | R. Kirk Collier, Jr. | Octane enhanced natural gas for internal combustion engine |
| US6405720B1 (en) | 2000-04-03 | 2002-06-18 | R. Kirk Collier, Jr. | Natural gas powered engine |
| US6508209B1 (en) | 2000-04-03 | 2003-01-21 | R. Kirk Collier, Jr. | Reformed natural gas for powering an internal combustion engine |
| US8025861B2 (en) | 2005-08-12 | 2011-09-27 | GM Global Technology Operations LLC | Making electrocatalyst supports for fuel cells |
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